Catalysts containing per-ortho aryl substituted aryl or heteroaryl substituted nitrogen donors

ABSTRACT

Catalyst compositions useful for the polymerization of olefins are disclosed. These compositions comprise a Group 8-10 metal complex comprising a bidentate or variable denticity ligand comprising one or two nitrogen donor atom or atoms independently substituted by an aromatic or heteroaromatic ring(s), wherein the ortho positions of said ring(s) are substituted by aryl or heteroaryl groups. Also disclosed are processes for the polymerization of olefins using the catalyst compositions.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of Provisional ApplicationNo. 60/231,920, filed on Sep. 11, 2000, under 35 USC § 119; the entirecontent of which is hereby incorporated by reference.

[0002] This application is also a continuation-in-part of applicationSer. No. 09/507,492, filed on Feb. 18, 2001, and Ser. No. 09/563,812,filed on May 3, 2000; the entire content of both applications is herebyincorporated by reference.

FIELD OF THE INVENTION

[0003] The present invention generally relates to catalyst compositionsuseful for the polymerization or oligomerization of olefins, and toprocesses using the catalyst compositions. Certain of these catalystcompositions comprise a Group 8-10 metal complex comprising a bidentateor variable denticity ligand comprising one or two nitrogen donor atomor atoms independently substituted by an aromatic or heteroaromaticring(s), wherein the ortho positions of said ring(s) are substituted byaryl or heteroaryl groups.

BACKGROUND OF THE INVENTION

[0004] Olefin polymers are used in a wide variety of products, fromsheathing for wire and cable to film. Olefin polymers are used, forinstance, in injection or compression molding applications, in extrudedfilms or sheeting, as extrusion coatings on paper, for examplephotographic paper and digital recording paper, and the like.Improvements in catalysts have made it possible to better controlpolymerization processes and, thus, influence the properties of the bulkmaterial. Increasingly, efforts are being made to tune the physicalproperties of plastics for lightness, strength, resistance to corrosion,permeability, optical properties, and the like, for particular uses.Chain length, polymer branching and functionality have a significantimpact on the physical properties of the polymer. Accordingly, novelcatalysts are constantly being sought in attempts to obtain a catalyticprocess for polymerizing olefins which permits more efficient andbetter-controlled polymerization of olefins.

[0005] The use of late transition metal complexes as catalysts forolefin polymerization has recently been reviewed by Ittel et al. (Chem.Rev. 2000, 100, 1169). Notwithstanding the many advances describedtherein, there remains a need for new late transition metal catalystsand processes with improved productivities under the elevatedtemperatures and pressures of commercial reactor operating conditions.New catalysts and processes for these purposes are described herein.

SUMMARY OF THE INVENTION

[0006] In a first aspect, this invention relates to a catalystcomposition useful for the polymerization of olefins, which comprises aGroup 8-10 metal complex comprising a bidentate or variable denticityligand comprising two nitrogen donor atoms independently substituted byaromatic or heteroaromatic rings, wherein the ortho positions of therings are substituted by aryl or heteroaryl groups.

[0007] In a second aspect, this invention relates to a catalystcomposition comprising either (i) a compound of formula ee1, (ii) thereaction product of a metal complex of formula ff1 and a second compoundY, or (iii) the reaction product of Ni(1,5-cyclooctadiene)₂, B(C₆F₅)₃, aligand selected from Set 18, and optionally an olefin;

[0008] wherein:

[0009] L² is selected from Set 18;

[0010] T is H, hydrocarbyl, substituted hydrocarbyl, or other groupcapable of inserting an olefin;

[0011] L is an olefin or a neutral donor group capable of beingdisplaced by an olefin; in addition, T and L may be taken together toform a π-allyl or π-benzyl group;

[0012] X⁻ is BF₄ ⁻, B(C₆F₅)₄ ⁻, BPh₄ ⁻, or another weakly coordinatinganion;

[0013] Q and W are each independently fluoro, chloro, bromo or iodo,hydrocarbyl, substituted hydrocarbyl, heteroatom attached hydrocarbyl,heteroatom attached substituted hydrocarbyl, or collectively sulfate, ormay be taken together to form a π-allyl, π-benzyl, or acac group, inwhich case a weakly coordinating counteranion X⁻ is also present;

[0014] Y is either (i) a metal hydrocarbyl capable of abstracting acacfrom ff1 in exchange for alkyl or another group capable of inserting anolefin, (ii) a neutral Lewis acid capable of abstracting Q⁻ or W⁻ fromff1 to form a weakly coordinating anion, a cationic Lewis acid whosecounterion is a weakly coordinating anion, or a Bronsted acid whoseconjugate base is a weakly coordinating anion, or (iii) a Lewis acidcapable of reacting with a π-allyl or π-benzyl group, or a substituentthereon, in ff1 to initiate olefin polymerization;

[0015] R^(3a,b) are each independently H, alkyl, hydrocarbyl,substituted hydrocarbyl, 2,4,6-triphenylphenyl, heteroatom connectedhydrocarbyl, heteroatom connected substituted hydrocarbyl, orfluoroalkyl; and

[0016] Ar^(1a-d) are each independently phenyl, 4-alkylphenyl,4-tert-butylphenyl, 4-trifluoromethylphenyl, 4-hydroxyphenyl,4-(heteroatom attached hydrocarbyl)-phenyl, 4-(heteroatom attachedsubstituted hydrocarbyl)-phenyl, or 1-naphthyl.

[0017] In a first preferred embodiment of this second aspect, the metalcomplex of formula ff1 is selected from Set 19;

[0018] wherein:

[0019] R^(3a,b) are each independently H, methyl, phenyl,4-methoxyphenyl, or 4-tert-butylphenyl;

[0020] Ar^(1a-d) are each independently phenyl, 4-methylphenyl,4-tert-butylphenyl, 4-trifluoromethylphenyl, 1-naphthyl, 2-naphthyl, or4-phenylphenyl; and

[0021] X⁻ is BF₄ ⁻, B(C₆F₅)₄ ⁻, BPh₄ ⁻, or another weakly coordinatinganion.

[0022] In a second preferred embodiment of this second aspect, thesubstituents Ar^(1a-d) are 4-tert-butylphenyl or 1-naphthyl. In a third,especially preferred, embodiment, the catalyst composition furthercomprises a solid support.

[0023] In a third aspect, this invention relates to a process for thepolymerization of olefins, comprising contacting one or more olefinswith the catalyst composition of the second aspect. In a preferredembodiment, of this second aspect, the second compound Y istrimethylaluminum, and the metal complex is contacted with thetrimethylaluminum in a gas phase olefin polymerization reactor.

[0024] In a fourth aspect, this invention relates to a compound offormula ii1;

[0025] wherein:

[0026] R^(3a,b) are each independently H, methyl, phenyl,4-methoxyphenyl, or 4-tert-butylphenyl; and

[0027] Ar^(1a-d) are each independently phenyl, 4-methylphenyl,4-tert-butylphenyl, 4-trifluoromethylphenyl, 1-naphthyl, 2-naphthyl, or4-phenylphenyl. Compounds of this formula are useful as ligands inconstituting the catalysts of the present invention.

[0028] In a fifth aspect, the invention relates to a process for thepolymerization of olefins, comprising contacting one or more olefinswith a catalyst composition comprising a Group 8-10 transition metalcomplex which comprises a ligand selected from Set 20;

[0029] wherein:

[0030] R^(2x,y) are each independently H, hydrocarbyl, substitutedhydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connectedsubstituted hydrocarbyl; in addition, R^(2x) and R^(2y) may be linked bya bridging group;

[0031] R^(3a-f) are each independently H, alkyl, hydrocarbyl,substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatomconnected substituted hydrocarbyl, or fluoroalkyl; and

[0032] Ar^(1a-d) are each independently phenyl, 4-alkylphenyl,4-tert-butylphenyl, 4-trifluoromethylphenyl, 4-hydroxyphenyl,4-(heteroatom attached hydrocarbyl)-phenyl, 4-(heteroatom attachedsubstituted hydrocarbyl)-phenyl, 1-naphthyl, 2-naphthyl, 9-anthracenyl,or aryl.

[0033] In a sixth aspect, this invention relates to a compound selectedfrom Set 21;

[0034] wherein:

[0035] R^(2x,y) are each independently H, hydrocarbyl, substitutedhydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connectedsubstituted hydrocarbyl; in addition, R^(2x) and R^(2y) may be linked bya bridging group;

[0036] R^(3a-f) are each independently H, alkyl, hydrocarbyl,substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatomconnected substituted hydrocarbyl, or fluoroalkyl; and

[0037] Ar^(1a-d) are each independently phenyl, 4-alkylphenyl,4-tert-butylphenyl, 4-trifluoromethylphenyl, 4-hydroxyphenyl,4-(heteroatom attached hydrocarbyl)-phenyl, 4-(heteroatom attachedsubstituted hydrocarbyl)-phenyl, 1-naphthyl, 2-naphthyl, 9-anthracenyl,or aryl. These compounds are are useful as ligands in constituting thecatalysts of the present invention.

[0038] In a seventh aspect, this invention relates to a catalystcomposition useful for the polymerization of olefins, which comprises aGroup 8-10 transition metal complex comprising a N,N-donor ligand of theformula kk1 or kk2;

[0039] wherein:

[0040] Ar^(2a,b) are each independently aromatic or heteroaromaticgroups wherein the ortho positions are substituted by aryl or heteroarylgroups;

[0041] M¹ is a metal selected from Groups 3, 4, 5, 6, 13, or 14, or isCu, P or As; and

[0042] L_(n) are ancillary ligands or groups which satisfy the valencyof M¹, such that M¹ is either a neutral, monoanionic or cationic metalcenter, or is a neutral or cationic P or As, with suitable counterionssuch that said catalyst composition has no net charge. M¹L_(n) may alsobe an active site for olefin polymerization. The compounds of formulakk2 are capable of ligating to two Group 8-10 metal centers, which maybe the same or different, where one or both of said Group 8-10 metalcenters may be active sites for olefin polymerization.

[0043] In an eighth aspect, this invention relates to a process for thepolymerization of olefins, comprising contacting one or more olefinswith the catalyst composition the seventh aspect.

[0044] We have surprisingly found that the catalyst compositions of thepresent invention can provide improved stability in the presence of anamount of hydrogen effective to achieve chain transfer, a totalproductivity greater than about 28,000 kg polyethylene per mole ofcatalyst at an operating temperature of at least 60° C. (preferablygreater than 56,000 kg PE/mol catalyst), and/or a higher productivity inthe presence of an amount of hydrogen effective to achieve chaintransfer, relative to the productivity observed in the absence ofhydrogen.

DETAILED DESCRIPTION OF THE INVENTION

[0045] In this disclosure, symbols ordinarily used to denote elements inthe Periodic Table and commonly abbreviated groups, take their ordinarymeaning, unless otherwise specified. Thus, N, O, S, P, and Si stand fornitrogen, oxygen, sulfur, phosphorus, and silicon, respectively, whileMe, Et, Pr, ^(i)Pr, Bu, ^(t)Bu and Ph stand for methyl, ethyl, propyl,iso-propyl, butyl, tert-butyl and phenyl, respectively.

[0046] A “hydrocarbyl” group means a monovalent or divalent, linear,branched or cyclic group which contains only carbon and hydrogen atoms.Examples of monovalent hydrocarbyls include the following: C₁-C₂₀ alkyl;C₁-C₂₀ alkyl substituted with one or more groups selected from C₁-C₂₀alkyl, C₃-C₈ cycloalkyl, and aryl; C₃-C₈ cycloalkyl; C₃-C₈ cycloalkylsubstituted with one or more groups selected from C₁-C₂₀ alkyl, C₃-C₈cycloalkyl, and aryl; C₆-C₁₄ aryl; and C₆-C₁₄ aryl substituted with oneor more groups selected from C₁-C₂₀ alkyl, C₃-C₈ cycloalkyl, and aryl.Examples of divalent (bridging) hydrocarbyls include: —CH₂—, —CH₂CH₂—,—CH₂CH₂CH₂—, and 1,2-phenylene.

[0047] The term “aryl” refers to an aromatic carbocyclic monoradical,which may be substituted or unsubstituted, wherein the substituents arehalo, hydrocarbyl, substituted hydrocarbyl, heteroatom attachedhydrocarbyl, heteroatom attached substituted hydrocarbyl, nitro, cyano,fluoroalkyl, sulfonyl, and the like. Examples include: phenyl, naphthyl,anthracenyl, phenanthracenyl, 2,6-diphenylphenyl, 3,5-dimethylphenyl,4-nitrophenyl, 3-nitrophenyl, 4-methoxyphenyl, 4-dimethylaminophenyl,and the like.

[0048] A “heterocyclic ring” refers to a carbocyclic ring wherein one ormore of the carbon atoms has been replaced by an atom selected from thegroup consisting of O, N, S, P, Se, As, Si, B, and the like.

[0049] A “heteroaromatic ring” refers to an aromatic heterocycle;examples include pyrrole, furan, thiophene, indene, imidazole, oxazole,isoxazole, carbazole, thiazole, pyrimidine, pyridine, pyridazine,pyrazine, benzothiophene, and the like.

[0050] A “heteroaryl” refers to a heterocyclic monoradical which isaromatic; examples include 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, furyl,thienyl, indenyl, imidazolyl, oxazolyl, isoxazolyl, carbazolyl,thiazolyl, pyrimidinyl, pyridyl, pyridazinyl, pyrazinyl, benzothienyl,and the like, and substituted derivatives thereof.

[0051] A “silyl” group refers to a SiR₃ group wherein Si is silicon andR is hydrocarbyl or substituted hydrocarbyl or silyl, as in Si(SiR₃)₃.

[0052] A “boryl” group refers to a BR₂ or B(OR)₂ group, wherein R ishydrocarbyl or substituted hydrocarbyl.

[0053] A “heteroatom” refers to an atom other than carbon or hydrogen.Preferred heteroatoms include oxygen, nitrogen, phosphorus, sulfur,selenium, arsenic, chlorine, bromine, silicon, and fluorine.

[0054] A “substituted hydrocarbyl” refers to a monovalent, divalent, ortrivalent hydrocarbyl substituted with one or more heteroatoms. Examplesof monovalent substituted hydrocarbyls include:2,6-dimethyl-4-methoxyphenyl, 2,6-diisopropyl-4-methoxyphenyl,4-cyano-2,6-dimethylphenyl, 2,6-dimethyl-4-nitrophenyl,2,6-difluorophenyl, 2,6-dibromophenyl, 2,6-dichlorophenyl,4-methoxycarbonyl-2,6-dimethylphenyl, 2-tert-butyl-6-chlorophenyl,2,6-dimethyl-4-phenylsulfonylphenyl,2,6-dimethyl-4-trifluoromethylphenyl,2,6-dimethyl-4-trimethylammoniumphenyl (associated with a weaklycoordinated anion), 2,6-dimethyl-4-hydroxyphenyl, 9-hydroxyanthr-10-yl,2-chloronapth-1-yl, 4-methoxyphenyl, 4-nitrophenyl, 9-nitroanthr-10-yl,—CH₂OCH₃, cyano, trifluoromethyl, and fluoroalkyl. Examples of divalent(bridging) substituted hydrocarbyls include: 4-methoxy-1,2-phenylene,1-methoxymethyl-1,2-ethanediyl, 1,2-bis(benzyloxymethyl)-1,2-ethanediyl,and 1-(4-methoxyphenyl)-1,2-ethanediyl. Examples of trivalenthydrocarbyls include methine and phenyl-substituted methane.

[0055] A “heteroatom connected hydrocarbyl” refers to a group of thetype E¹⁰(hydrocarbyl), E²⁰H(hydrocarbyl), or E²⁰(hydrocarbyl)₂, whereE¹⁰ is an atom selected from Group 16 and E²⁰ is an atom selected fromGroup 15.

[0056] A “heteroatom connected substituted hydrocarbyl” refers to agroup of the type E¹⁰(substituted hydrocarbyl), E²⁰H(substitutedhydrocarbyl), or E²⁰(substituted hydrocarbyl)₂, where E¹⁰ is an atomselected from Group 16 and E²⁰ is an atom selected from Group 15.

[0057] The term “fluoroalkyl” as used herein refers to a C₁-C₂₀ alkylgroup substituted by one or more fluorine atoms.

[0058] An “olefin” refers to a compound of the formulaR^(1a)CH═CHR^(1b), where R^(1a) and R^(1b) may independently be H,hydrocarbyl, substituted hydrocarbyl, fluoroalkyl, silyl,O(hydrocarbyl), or O(substituted hydrocarbyl), and where R^(1a) andR^(1b) may be connected to form a cyclic olefin, provided that in allcases, the substituents R^(1a) and R^(1b) are compatible with thecatalyst. In the case of most Group 4-7 catalysts, this will generallymean that the olefin should not contain good Lewis base donors, sincethis will tend to severely inhibit catalysis. Preferred olefins for suchcatalysts include ethylene, propylene, butene, hexene, octene,cyclopentene, norbornene, and styrene.

[0059] In the case of the Group 8-10 catalysts, Lewis basic substituentson the olefin will tend to reduce the rate of catalysis in most cases;however, useful rates of homopolymerization or copolymerization cannonetheless be achieved with some of those olefins. Preferred olefinsfor such catalysts include ethylene, propylene, butene, hexene, octene,and fluoroalkyl substituted olefins, but may also include, in the caseof palladium and some of the more functional group tolerant nickelcatalysts, norbornene, substituted norbornenes (e.g., norbornenessubstituted at the 5-position with halide, siloxy, silane, halo carbon,ester, acetyl, alcohol, or amino groups), cyclopentene, ethylundecenoate, acrylates, vinyl ethylene carbonate,4-vinyl-2,2-dimethyl-1,3-dioxolane, and vinyl acetate.

[0060] In some cases, the Group 8-10 catalysts can be inhibited byolefins which contain additional olefinic or acetylenic functionality.This is especially likely if the catalyst is prone to “chain-running”wherein the catalyst can migrate up and down the polymer chain betweeninsertions, since this can lead to the formation of relativelyunreactive π-allylic intermediates when the olefin monomer containsadditional unsaturation. Such effects are best determined on acase-by-case basis, but may be predicted to some extent throughknowledge of how much branching is observed with a given catalyst inethylene homopolymerizations; those catalysts which tend to giverelatively high levels of branching with ethylene will tend to exhibitlower rates when short chain diene co-monomers are used under the sameconditions. Longer chain dienes tend to be less inhibitory than shorterchain dienes, when other factors are kept constant, since the catalysthas farther to migrate to form the π-allyl, and another insertion mayintervene first.

[0061] Similar considerations apply to unsaturated esters which arecapable of inserting and chain-running to form relatively stableintramolecular chelate structures wherein the Lewis basic esterfunctionality occupies a coordination site on the catalyst. In suchcases, short chain unsaturated esters, such as methyl acrylate, tend tobe more inhibitory than long chain esters, such as ethyl undecenoate, ifall other factors are kept constant.

[0062] A “π-allyl” group refers to a monoanionic group with three sp²carbon atoms bound to a metal center in a η³-fashion. Any of the threesp² carbon atoms may be substituted with a hydrocarbyl, substitutedhydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connectedsubstituted hydrocarbyl, or O-silyl group. Examples of π-allyl groupsinclude:

[0063] The term π-benzyl group denotes an π-allyl group where two of thesp² carbon atoms are part of an aromatic ring. Examples of π-benzylgroups include:

[0064] A “bridging group” refers to an atom or group which links two ormore groups, which has an appropriate valency to satisfy itsrequirements as a bridging group, and which is compatible with thedesired catalysis. Suitable examples include divalent or trivalenthydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl,heteroatom connected substituted hydrocarbyl, substituted silicon(IV),boron(III), N(III), P(III), and P(V), —C(O)—, —SO₂—, —C(S)—, —B(OMe)—,—C(O)C(O)—, O, S, and Se. In some cases, the groups which are said to be“linked by a bridging group” are directly bonded to one another, inwhich case the term “bridging group” is meant to refer to that bond. By“compatible with the desired catalysis,” we mean a bridging group orsubstituent which either does not interfere with the desired catalysis,or acts to usefully modify the catalyst activity or selectivity.

[0065] The term “weakly coordinating anion” is well known in the art perse and generally refers to a large bulky anion capable of delocalizationof the negative charge of the anion. Weakly coordinating anions, not allof which would be considered bulky, include, but are not limited to:B(C₆F₅)₄ ⁻, PF₆ ⁻, BF₄ ⁻, SbF₆ ⁻, (F₃CSO₂)₂N⁻, (F₃CSO₂)₃C⁻, (Ph)₄B⁻wherein Ph=phenyl, and Ar₄B⁻ whereinAr₄B⁻=tetrakis[3,5-bis(trifluoromethyl)phenyl]-borate. The weaklycoordinating nature of such anions is known and described in theliterature (S. Strauss et al., Chem. Rev., 1993, 93, 927).

[0066] The term “ortho” is used herein in the context of the ligands ofthe present invention to denote the positions which are adjacent to thepoint of attachment of the aromatic or heteroaromatic ring to theligated nitrogen(s). In the case of a 1-attached, 6-membered ring, wemean the 2- and 6-positions. In the case of a 1-attached, 5-memberedring, we mean the 2- and 5-positions. In the case of 1-attached, fusedring aromatic or heteroaromatic rings, we mean the first positions whichcan be substituted; for example, in the case of 1-naphthyl, these wouldbe the 2- and 8-positions; in the case of 9-anthracenyl, these would bethe 1- and 8-positions.

[0067] The term “variable denticity” is used herein in the context ofotherwise bidentate ligands to refer to the reversible formation of athird binding interaction between the ligand and the Group 8-10transition metal center to which it is complexed.

[0068] The abbreviation “acac” refers to acetylacetonate. In general,substituted acetylacetonates, wherein one or more hydrogens in theparent structure have been replaced by a hydrocarbyl, substitutedhydrocarbyl, or fluoroalkyl, may be used in place of the “acac”.Hydrocarbyl substituted acetylacetonates may be preferred in some caseswhen it is important, for example, to improve the solubility of a(ligand)Ni(acac)BF₄ salt in mineral spirits.

[0069] The phrase “an amount of hydrogen effective to achieve chaintransfer” refers to the ability of hydrogen to react with an olefinpolymerization catalyst to cleave off a growing polymer chain andinitiate a new chain. In most cases, this is believed to involvehydrogenolysis of the metal-carbon bond of the growing polymer chain, toform a metal hydride catalytic intermediate, which can then react withthe olefin monomer to initiate a new chain. In the context of thecurrent invention, an effective amount is considered to be that amountof hydrogen which reduces both the number average molecular weight andthe weight average molecular weight of the polymer by at least 10%,relative to an otherwise similar reaction conducted in the absence ofhydrogen. In this context, “otherwise similar” denotes that thecatalyst, catalyst loading, solvent, solvent volume, agitation, ethylenepressure, co-monomer concentration, reaction time, and other processrelevant parameters are sufficiently similar that a valid comparison canbe made.

[0070] In general, previously reported catalysts lacking the novelortho-aryl substitution pattern of the current invention are far lessproductive in the presence of an amount of hydrogen effective to achievechain transfer than they are under otherwise similar conditions withouthydrogen. In order to quantify this effect, the following terms aredefined.

[0071] The productivity P is defined as the grams of polymer producedper mole of catalyst, over a given period of time. The productivityP_(hydrogen) is defined as the grams of polymer produced per mole ofcatalyst in the presence of an amount of hydrogen effective to achievechain transfer, in an otherwise similar reaction conducted for the sameperiod of time. Catalysts lacking the novel ortho-aryl substitutionpattern of the catalyst compositions of the current invention typicallyexhibit ratios P_(hydrogen)/P less than or equal to 0.05 undersubstantially non-mass transport limited conditions.

[0072] The phrase “improved stability in the presence of an amount ofhydrogen effective to achieve chain transfer” means that the ratioP_(hydrogen)/P is at least 0.1 under substantially non-mass transportlimited conditions. Preferred catalysts of the present invention exhibita ratio P_(hydrogen)/P greater than or equal to 0.2 under substantiallynon-mass transport limited conditions. Especially preferred catalysts ofthe present invention exhibit a ratio P_(hydrogen)/P greater than orequal to 0.5 under substantially non-mass transport limited conditions.

[0073] The phrase “one or more olefins” refers to the use of one or morechemically different olefin monomer feedstocks, for example, ethyleneand propylene.

[0074] The phrase “capable of inserting an olefin” refers to a group Zbonded to the transition metal M, which can insert an olefin monomer ofthe type R^(1a)CH═CHR^(1b) to form a moiety of the typeM—CHR^(1a)—CHR^(1b)—Z, which can subsequently undergo further olefininsertion to form a polymer chain; wherein R^(1a) and R^(1b) mayindependently be H, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl,silyl, O(hydrocarbyl), or O(substituted hydrocarbyl), and wherein R^(1a)and R^(1b) may be connected to form a cyclic olefin, provided that inall cases, the substituents R^(1a) and R^(1b) are compatible with thedesired catalysis; wherein additional groups will be bound to thetransition metal M to comprise the actual catalyst, as discussed in moredetail below.

[0075] The degree of steric hindrance at the active catalyst siterequired to give slow chain transfer, and thus form polymer, depends ona number of factors and is often best determined by experimentation.These factors include: the exact structure of the catalyst, the monomeror monomers being polymerized, whether the catalyst is in solution orattached to a solid support, and the temperature and pressure. The term“polymer” is defined herein as corresponding to a degree ofpolymerization, DP, of about 10 or more; oligomer is defined ascorresponding to a DP of 2 to about 10.

[0076] The term “total productivity” is defined in the context ofethylene polymerization as the number of kilograms of polyethylene permole of catalyst and is the maximum weight of polyethylene that can beproduced using a given catalyst.

[0077] By “suitable counterions”, we mean weakly coordinating ions withsufficient charge to give the overall catalyst complex no net charge.

[0078] In the context of structures kk1 and kk2, “ancillary ligands” areatoms or groups which serve to satisfy the valency of M¹ withoutinterfering with the desired catalysis.

[0079] The compounds of Sets 18-21 and formula ii1 may be prepared asdescribed in the examples contained herein, or by methods described inthe references cited by Ittel et al. (Chem. Rev. 2000, 100, 1169); or inU.S. patent application Ser. No. 09/507,492, filed on Feb. 18, 2000,Ser. No. 09/563,812, filed on May 3, 2000, and Ser. No. 09/231,920,filed on Sep. 11, 2000; or in U.S. Provisional Application Nos.60/246,254, 60/246,255, and 60/246,178, all filed on Nov. 6, 2000.

[0080] A variety of protocols may be used to generate activepolymerization catalysts comprising transition metal complexes ofvarious nitrogen, phosphorous, oxygen and sulfur donor ligands. Examplesinclude: (i) the reaction of a Ni(II), Pd(II), Co(II) or Fe(II) dihalidecomplex of a bidentate N,N-donor ligand with an alkylaluminum reagent,for example, the reaction of (bidentate N,N-donor ligand)Ni(acac)X saltswith an alkylaluminum reagent, where X is a weakly coordinating anion,such as B(C₆F₅)₄ ⁻, BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻ and OS(O)₂CF₃ ⁻, (ii) thereaction of a bidentate N,N-donor ligand withbis(1,5-cyclooctadiene)nickel(0) and [H(OEt₂)₂]⁺[B(3,5-(CF₃)₂C₆H₃)₄]⁻,and (iii) the reaction of a bidentate N,N-donor ligand withbis(1,5-cyclooctadiene)nickel(0) and B(C₆F₅)₃. Cationic[(ligand)M(π-allyl)]⁺ complexes with weakly coordinating counteranions,where M is a Group 10 transition metal, are often also suitable catalystprecursors, requiring only exposure to olefin monomer and in some caseselevated temperatures (40-100° C.) or added Lewis acid, or both, to forman active polymerization catalyst.

[0081] More generally, a variety of (ligand)_(n)M(Z^(1a))(Z^(1b))complexes, where “ligand” refers to a compound of the present inventionand is a bidentate or variable denticity ligand comprising one or twonitrogen donor atom or atoms independently substituted by an aromatic orheteroaromatic ring(s), wherein the ortho positions of the ring(s) aresubstituted by aryl or heteroaryl groups, n is 1 or 2, M is a Group 8-10transition metal, and Z^(1a) and Z^(1b) are univalent groups, or may betaken together to form a divalent group, may be reacted with one or morecompounds, collectively referred to as compound Y, which function asco-catalysts or activators, to generate an active catalyst of the form[(ligand)_(n)M(T^(1a))(L)]⁺X⁻, where n is 1 or 2, T^(1a) is a hydrogenatom or hydrocarbyl, L is an olefin or neutral donor group capable ofbeing displaced by an olefin, M is a Group 8-10 transition metal, and X⁻is a weakly coordinating anion. When Z^(1a) and Z^(1b) are both halide,examples of compound Y include: methylaluminoxane (herein MAO) and otheraluminum sesquioxides, R₃Al, R₂AlCl, and RAlCl₂ (wherein R is alkyl, andplural groups R may be the same or different). When Z^(1a) and Z^(1b)are both alkyl, examples of a compound Y include: MAO and other aluminumsesquioxides, R₃Al, R₂AlCl, RAlCl₂ (wherein R is alkyl, and pluralgroups R may be the same or different), B(C₆F₅)₃, R⁰ ₃Sn[BF₄] (whereinR⁰ is hydrocarbyl or substituted hydrocarbyl and plural groups R⁰ may bethe same or different), H⁺X⁻, wherein X⁻ is a weakly coordinating anion,for example, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and Lewisacidic or Bronsted acidic metal oxides, for example, montmorilloniteclay. In some cases, for example, when Z^(1a) and Z^(1b) are both halideor carboxylate, sequential treatment with a metal hydrocarbyl, followedby reaction with a Lewis acid, may be required to generate an activecatalyst. Examples of metal hydrocarbyls include: MAO, other aluminumsesquioxides, R₃Al, R₂AlCl, RAlCl₂ (wherein R is alkyl, and pluralgroups R may be the same or different), Grignard reagents, organolithiumreagents, and diorganozinc reagents. Examples of Lewis acids include:MAO, other aluminum sesquioxides, R₃Al, R₂AlCl, RAlCl₂ (wherein R isalkyl, and plural groups R may be the same or different), B(C₆F₅)₃, R⁰₃Sn[BF₄] (wherein R⁰ is hydrocarbyl or substituted hydrocarbyl andplural groups R⁰ may be the same or different), and Lewis acidic metaloxides.

[0082] The foregoing discussion is intended to illustrate that there arefrequently many ways to generate an active catalyst. There are a varietyof methods wherein the ligands of the present invention can be reactedwith a suitable metal precursor, and optionally a co-catalyst, togenerate an active olefin polymerization catalyst. Without wishing to bebound by theory, we believe that the active catalyst typically comprisesthe catalytically active metal, one or more ligands of the presentinvention, the growing polymer chain (or a hydride capable of initiatinga new chain), and a site on the metal adjacent to the metal-alkyl bondof said chain where ethylene can coordinate, or at least closelyapproach, prior to insertion. Where specific structures for activecatalysts have been implied herein, it should be understood that activecatalysts comprising the ligands of the present invention are formed asthe reaction products of the catalyst activation reactions disclosedherein, regardless of the detailed structures of those active species.

[0083] In some cases, it is advantageous to attach the catalyst to asolid support. Examples of useful solid supports include: inorganicoxides, such as talcs, silicas, titania, silica/chromia,silica/chromia/titania, silica/alumina, zirconia, aluminum phosphategels, silanized silica, silica hydrogels, silica xerogels, silicaaerogels, montmorillonite clay and silica co-gels, as well as organicsupport materials such as polystyrene and functionalized polystyrene.(See, for example, S. B. Roscoe et al., “Polyolefin Spheres fromMetallocenes Supported on Non-Interacting Polystyrene,” 1998, Science,280, 270-273 (1998)).

[0084] Thus, in a preferred embodiment, the catalysts of the presentinvention are attached to a solid support (by “attached to a solidsupport” is meant ion paired with a component on the surface, adsorbedto the surface or covalently attached to the surface) that has beenpre-treated with a compound Y. More generally, the compound Y and thesolid support can be combined in any order and any number of compound(s)Y can be utilized. In addition, the supported catalyst thus formed maybe treated with additional quantities of compound Y. In anotherpreferred embodiment, the compounds of the present invention areattached to silica that has been pre-treated with an alkylaluminumcompound Y, for example, MAO, Et₃Al, ^(i)Bu₃Al, Et₂AlCl, or Me₃Al.

[0085] Such supported catalysts are prepared by contacting thetransition metal compound, in a substantially inert solvent (by which ismeant a solvent which is either unreactive under the conditions ofcatalyst preparation, or if reactive, acts to usefully modify thecatalyst activity or selectivity) with MAO-treated silica for asufficient period of time to generate the supported catalyst. Examplesof substantially inert solvents include toluene, o-difluorobenzene,mineral spirits, hexane, CH₂Cl₂, and CHCl₃.

[0086] In another preferred embodiment, the catalysts of the presentinvention are activated in solution under an inert atmosphere, and thenadsorbed onto a silica support which has been pre-treated with asilylating agent to replace surface silanols by trialkylsilyl groups.Methods to pre-treat silicas in this way are known to those skilled inthe art and may be achieved, for example, by heating the silica withhexamethyldisilazane and then removing the volatiles under vacuum. Avariety of precurors and procedures may be used to generate theactivated catalyst prior to said adsorption, including, for example,reaction of a (ligand)Ni(acac)B(C₆F₅)₄ complex with Et₂AlCl in atoluene/hexane mixture under nitrogen; where “ligand” refers to acompound of the present invention.

[0087] The polymerizations may be conducted in batch or continuousprocesses, as solution polymerizations, as non-solvent slurry typepolymerizations, as slurry polymerizations using one or more of theolefins or other solvent as the polymerization medium, or in the gasphase. One of ordinary skill in the art, with the present disclosure,would understand that the catalyst could be supported using a suitablecatalyst support and methods known in the art. Substantially inertsolvents, such as toluene, hydrocarbons, methylene chloride and thelike, may be used. Propylene and 1-butene are excellent monomers for usein slurry-type copolymerizations and unused monomer can be flashed offand reused.

[0088] Temperature and olefin pressure have significant effects onpolymer structure, composition, and molecular weight. Suitablepolymerization temperatures are preferably from about 20° C. to about160° C., more preferably 60° C. to about 100° C. Suitable polymerizationpressures range from about 1 bar to 200 bar, preferably 5 bar to 50 bar,and more preferably from 10 bar to 50 bar.

[0089] The catalyst concentration in solution, or loading on a support,is adjusted to give a level of activity suitable for the process anddesired polymer. In the case of solution phase or a slurry phase processusing a soluble catalyst precursor, suitable catalyst concentrations aretypically in the range of 0.01 to 100 micromoles/L, preferably 0.1 to 10micromoles/L, even more preferably 0.2 to 2 micromoles/L. Higherloadings tend to reduce the solution phase concentration of ethylene ata given temperature, pressure and agitation rate, and can thereforeresult in relatively more chain running and branching in some cases.

[0090] In some cases, it is possible that the catalysts of the presentinvention may acquire new hydrocarbyl substituents, attached to theligand or counteranion, or both, under the conditions of the olefinpolymerization reaction. For example, if a bidentate N,N-donor ligand ofthe current invention underwent cyclometallation to form a tridentateligand with a nickel-carbon bond, insertion of one or more ethylenesinto this bond, followed by hydrogenolysis or by β-H elimnation, couldresult in a new hydrocarbyl side chain attached to said ligand.Alternatively, the ligand could comprise an olefinic side chainsubstituent prior to polymerization, and this side chain could undergocopolymerization in the presence of ethylene to attach an oligomeric orpolymeric group to the ligand. It is also possible that the reactionproduct of (i) bis(1,5-cyclooctadiene)nickel(0), (ii) a ligand of thepresent invention and (iii) B(C₆F₅)₃ may comprise acycloctadiene-derived hydrocarbyl bridge between cationic nickel andanionic boron, and subsequent ethylene insertion may result in theattachment of a polyethylene chain to the borate counteranion.Therefore, although hydrocarbyl groups attached to the ligand orcounteranion of the current invention will generally be relatively lowmolecular weight groups (less than about MW=500), it is possible thatthey will be modified as described above under some olefinpolymerization reaction conditions, and any such modified catalysts arealso considered within the scope of this invention.

[0091] The catalysts of the present invention may be used alone, or incombination with one or more other Group 3-10 olefin polymerization oroligomerization catalysts, in solution, slurry, or gas phase processes.Such mixed catalysts systems are sometimes useful for the production ofbimodal or multimodal molecular weight or compositional distributions,which may facilitate polymer processing or final product properties.

[0092] After the reaction has proceeded for a time sufficient to producethe desired polymers, the polymer can be recovered from the reactionmixture by routine methods of isolation and/or purification.

[0093] In general, the polymers of the present invention are useful ascomponents of thermoset materials, as elastomers, as packagingmaterials, films, compatibilizing agents for polyesters and polyolefins,as a component of tackifying compositions, and as a component ofadhesive materials.

[0094] High molecular weight resins are readily processed usingconventional extrusion, injection molding, compression molding, andvacuum forming techniques well known in the art. Useful articles madefrom them include films, fibers, bottles and other containers, sheeting,molded objects and the like.

[0095] Low molecular weight resins are useful, for example, as syntheticwaxes and they may be used in various wax coatings or in emulsion form.They are also particularly useful in blends with ethylene/vinyl acetateor ethylene/methyl acrylate-type copolymers in paper coating or inadhesive applications.

[0096] Although not required, typical additives used in olefin or vinylpolymers may be used in the new homopolymers and copolymers of thisinvention. Typical additives include pigments, colorants, titaniumdioxide, carbon black, antioxidants, stabilizers, slip agents, flameretarding agents, and the like. These additives and their use in polymersystems are known per se in the art.

[0097] Other features of the invention will become apparent in thefollowing description of working examples, which have been provided forillustration of the invention and are not intended to be limitingthereof.

[0098] The molecular weight data presented in the following examples isdetermined at 135° C. in 1,2,4-trichlorobenzene using refractive indexdetection, calibrated using narrow molecular weight distributionpoly(styrene) standards.

EXAMPLES Example 1

[0099] Synthesis of aaa1

[0100] To a 500 mL round bottomed flask equipped with a magnetic stirbar was added 25 g (141.8 mmol) of 4′-tert-butylacetophenone and 7.52 g(70.9 mmol) of benzaldehyde. The solution was stirred and 20.9 mL (170.2mmol) of boron trifluoride diethyl etherate was added dropwise. Thesolution was stirred for 1 h at room temperature then the reactionvessel was lowered into a preheated oil bath at 90° C. and stirred for 2h. The reaction vessel was allowed to cool to room temperature thenpoured into 500 mL of diethyl ether. The product precipitated fromsolution and was isolated by suction filtration. The filter cake waswashed with 100 mL of diethyl ether then dried under vacuum to give11.30 g (31%) of aaa1 as a yellow solid. ¹H NMR (DMSO-d₆, 300 MHz) δ1.40(s, 18H), 7.81 (d, J=8.8 Hz, 4H), 7.82 (m, 3H), 8.50 (d, J=8.3 Hz, 4 H),8.57 (d, J=7.7 Hz, 2 H), 9.08 (s, 2H).

Example 2

[0101] Synthesis of aaa2

[0102] To a 500 mL round bottomed flask equipped with a magnetic stirbar and a reflux condenser was added 11.0 g (21.7 mmol) of aaa1, 100 mLof anhydrous ethanol, and 1.7 mL (32.5 mmol) of nitromethane. Themixture was stirred and 9.1 mL (65.1 mmol) of triethylamine was addedover 3 minutes. The reaction vessel was lowered into a preheated oilbath at 110° C. and allowed to reflux under nitrogen. After 1 h thereaction vessel was allowed to cool to room temperature and 100 mL ofmethanol was added to precipitate the product. The product was collectedby suction filtration, washed with 100 mL of methanol and dried undervacuum to give 6.42 g (64%) of aaa2 as a white solid. ¹H NMR (CDCl₃, 300MHz) δ1.36 (s, 18 H), 7.43 (m, 11 H), 7.62 (s, 2H), 7.62 (m, 1H), 7.64(m, 1H).

Example 3

[0103] Synthesis of aaa3

[0104] To a 300 mL Parr shaker vessel was added 6.4 g (13.8 mmol) ofaaa2 and a slurry of 1.28 g of 5% Pd/C in 50 mL of DMF followed by 30 mLof methanol. The reaction vessel was purged with nitrogen three times,heated to 50° C. and shaken under 55 psi of hydrogen for 12 h. Thereaction vessel was purged with nitrogen then allowed to cool to roomtemperature. The mixture was filtered through Celite and the Celite padwas washed with 100 ml of methylene chloride. The solution wasconcentrated to remove the methylene chloride then 400 mL of methanolwas added to precipitate the product. The product was collected bysuction filtration and washed with 100 mL of methanol to give 5.46 g(91%) of aaa3 as a white crystalline solid. ¹H NMR (CDCl₃, 300 MHz)δ1.39 (s, 18H), 3.98 (s, 2H), 7.26 (m, 2H), 7.40 (m, 4H), 7.51 (m, 7H),7.60 (m, 2H).

Example 4

[0105] Synthesis of aaa4

[0106] To a 500 mL round bottomed flask equipped with a magnetic stirbar was added 50 g (373 mmol) of 4′-methylacetophenone and 19.77 g(186.3 mmol) of benzaldehyde. The solution was stirred and 56.7 mL(447.12 mmol) of boron trifluoride diethyl etherate was added dropwise.The solution was stirred for 30 min at room temperature then thereaction vessel was lowered into a preheated oil bath at 90° C. andstirred for 2 h. The reaction vessel was allowed to cool to roomtemperature then poured into 1 L of diethyl ether. The productprecipitated from solution and was isolated by suction filtration. Thefilter cake was washed with 500 mL of diethyl ether then dried undervacuum to give 27.85 g (35%) of aaa4 as a yellow solid. ¹H NMR (CDCl₃,300 MHz) δ2.5 (s, 6H), 7.59 (d, J=7.9 Hz, 4H), 7.72 (m, 2H), 7.86 (m,1H), 8.47 (d, J=8.4 Hz, 4H), 8.56 (d, J=7.3 Hz, 2H), 9.04 (s, 2H).

Example 5

[0107] Synthesis of aaa5

[0108] To a 300 mL round bottomed flask equipped with a magnetic stirbar and a reflux condenser was added 27.0 g (63.7 mmol) of aaa4, 100 mLof anhydrous ethanol, and 4.92 mL (95.5 mmol) of nitromethane. Themixture was stirred and 26.6 mL (191.1 mmol) of triethylamine was added.The reaction vessel was lowered into a preheated oil bath at 110° C. andallowed to reflux under nitrogen. After 2.5 h the reaction vessel wasallowed to cool to room temperature and concentrated to an oil. The oilwas purified by silica gel chromatography (20% methylene chloride inhexane) to give 14.93 g (62%) of aaa5 as a colorless oil thatcrystallized upon standing. ¹H NMR (CDCl₃, 300 MHz) δ2.41 (s, 6H), 7.26(d, J=7.8 Hz, 4H), 7.36 (d, J=7.9 Hz, 4H), 7.46 (m, 3H), 7.61 (s, 2H),7.64 (m, 2H).

Example 6

[0109] Synthesis of aaa6

[0110] To a 300 mL Parr shaker vessel was added 17.6 g (46.4 mmol) ofaaa5 and a slurry of 1.76 g of 5% Pd/C in 60 mL of DMF followed by 30 mLof methanol. The reaction vessel was purged with nitrogen three times,heated to 50° C. and shaken under 55 psi of hydrogen for 6 h. Thereaction vessel was purged with nitrogen then allowed to cool to roomtemperature. The mixture was filtered through Celite and the Celite padwas washed with 100 ml of methylene chloride. The solution wasconcentrated to remove the methylene chloride then 500 mL of methanolwas added to precipitate the product. The product was collected bysuction filtration and washed with 100 mL of methanol to give 16.18 g(100%) of aaa6 as a white crystalline solid. ¹H NMR (CDCl₃, 300 MHz)δ2.49 (s, 6H), 3.99 (s, 2H), 7.34 (m, 1H), 7.36 (d, J=7.5 Hz, 4H), 7.44(d, J=8.0 Hz), 7.48 (s, 2H), 7.54 (d, J=7.8 Hz, 4H), 7.67 (d, J=8.1 Hz,2H).

Example 7

[0111] Synthesis of aaa7

[0112] Pyridine (25 mL) was added to a 100 mL round bottomed flaskequipped with a magnetic stir bar followed by 8.20 g (23.5 mmol) ofaaa6. The mixture was stirred and 1.03 mL (11.75 mmol) of oxalylchloride was added dropwise. The mixture was stirred for 2 h at roomtemperature then poured into 400 mL of methanol to precipitate theproduct. The product was isolated by suction filtration, washed with 100mL of methanol then dried under vacuum to give 5.28 g (60%) of aaa7 as alight blue solid. ¹H NMR (CDCl₃, 300 MHz) δ2.47 (s, 12H), 7.21 (s, 16H),7.45 (m, 6H), 7.62 (s, 4H), 7.66 (d, J=7.4 Hz, 4H), 8.71 (s, 2H).

Example 8

[0113] Synthesis of aaa8

[0114] To a 250 mL round bottomed flask equipped with a magnetic stirbar was added 5.25 g (6.98 mmol) of aaa7, 100 mL of o-xylene, and 3.10 gof P₄S₁₀. The reaction vessel was lowered into a preheated oil bath at150° C. and stirred under nitrogen for 1 h. The reaction vessel wasallowed to cool to room temperature then poured into 400 mL of methanolto precipitate the product. The product was isolated by suctionfiltration then washed with 100 mL of methanol then dried under vacuumto give 5.11 g (94%) of aaa8 as orange crystals. ¹H NMR (CDCl₃, 300 MHz)δ2.44 (s, 12H), 7.13 (d, J=7.9 Hz, 8H), 7.21 (d, J=8.5 Hz, 8H), 7.41 (m,6H), 7.61 (s, 4H), 7.65 (m, 4H), 11.2 (s, 2H).

Example 9

[0115] Synthesis of aaa9

[0116] To a 100 mL round bottomed flask equipped with a magnetic stirbar was added 5.00 g (6.38 mmol) of aaa8, 10 mL of 1,2-dibromoethane,and 10 mL of 6.4 M NaOH solution followed by 409 mg (1.27 mmol) oftetrabutylammonium bromide. The mixture was stirred for 15 minutes thenpoured into 150 mL of methanol to give an oil that gradually solidified.The solid was isolated by suction filtration, crushed with a spatulathen washed with 50 mL of methanol and dried under vacuum to give 5.14 g(100%) of aaa9 as a tan solid. ¹H NMR (CDCl₃, 300 MHz) δ2.16 (s, 4H),2.70 (s, 12H), 7.10 (d, J=7.9 Hz, 8H), 7.42 (m, 14 H), 7.62 (s, 4H),7.69 (d, J=7.3 HZ, 4H).

Example 10

[0117] Synthesis of aaa10

[0118] A suspension of dibenzoyl ethane (8.8 g, 37 mmol) in toluene (15ml) and 1-methyl-2-pyrrolidinone (7.5 ml) was treated with oxalicdihydrazide (2 g, 17 mmol). The flask was fitted with a Dean Stark trap,and immersed in a 170° C. oil bath. The resulting suspension was stirredunder Ar, with azeotropic removal of water until all of the startingdiketone was consumed (determined by TLC), then cooled to rt. Thesolvent was removed in vacuo. The dark oily residue was washed with MeOHand filtered to afford a mixture (4.21 g) ofN,N′-bis(2,5-diphenyl-1-pyrrolyl) oxamide contaminated with anunidentified impurity (on the order of 50-65% by weight), which was usedwithout purification.

Example 11

[0119] Synthesis of aaa11

[0120] A suspension of impure aaa10 from Example 10 (523 mg) inortho-xylene (6 ml) was treated with phosphorus pentasulfide (222 mg,0.5 mmol). The flask was fitted with a reflux condenser, and immersed ina 180° C. oil bath. The resulting suspension was refluxed under nitrogenfor ca. 2 h, then cooled to rt, then diluted with ca. 35 mL methylenechloride. The heterogeneous mixture was poured onto a column of silica(10″×50 mm) and eluted with methylene chloride/toluene (3/2), collectingonly the forerunning orange-red band. The solvent was removed in vacuoto give aaa11 as deep violet needles (yield 121 mg).

Example 12

[0121] Synthesis of aaa12

[0122] A suspension of aaa11 (566 mg, 1.02 mmol) in 1,2-dibromoethane (7ml) was treated with tetrabutylammonium bromide (15 mg) and 2 N aq NaOH(10 mL). The biphasic mixture was stirred vigorously for 15 min. Thecolor discharged markedly and a pale precipitate separated almostimmediately on stirring. The mixture was diluted with methylene chloride(200 mL) and water (200 mL). The layers were separated, and the organiclayer was washed with water (2×50 mL) and dried (MgSO₄), concentrated,and adsorbed onto silica, then chromatographed over silica eluting withmethylene chloride/hexane. The solvent was removed in vacuo to giveaaa12 as an orange-yellow powder (yield 520 mg).

Example 13

[0123] Synthesis of aaa13

[0124] aaa3 (5.1 g, 11.76 mmol) was dissolved in pyridine (5 mL) andtreated with 4-(dimethylamino)-pyridine (30 mg). Under an atmosphere ofdry nitrogen gas, oxalyl chloride (515 mL, 5.88 mmol) was addeddropwise. The mixture was stirred ca. 72 h at rt, then heated to 60 Cfor 2 h more. After cooling to rt, tlc analysis indicated that some ofthe aniline remained unreacted, but the desired product was the majorcomponent of the reaction mixture. The reaction mixture was treated withmethanol to precipitate the desired product. The white powder wascollected by vacuum filtration, and washed with methanol to afford 4.4 gaaa13.

Example 14

[0125] Synthesis of aaa14

[0126] A suspension of aaa13 (4.4 g, 4.78 mmol) in ortho-xylene (20 ml)was treated with phosphorus pentasulfide (1.1 g, 2.39 mmol). The flaskwas fitted with a reflux condenser, and immersed in a 180° C. oil bath.The resulting suspension was refluxed under nitrogen for ca. 3 h, thencooled to rt, then diluted with ca. 35 mL methylene chloride. Theheterogeneous mixture was poured onto a column of silica (10″×50 mm) andeluted with methylene chloride/hexane, collecting only the forerunningorange band. Upon concentration, aaa14 crystallized from solution asorange needles (2 g), and was collected by filtration. The filtrate wasconcentrated to give more aaa14 as an orange crystalline powder (1.8 g).

Example 15

[0127] Synthesis of aaa15

[0128] A suspension of aaa14 (2 g, 2.1 mmol) in 1,2-dibromoethane (7 ml)was treated with tetrabutylammonium bromide (15 mg) and 2 N aq NaOH (10mL). The biphasic mixture was stirred vigorously for 1.5 h. The colordischarged markedly and a pale precipitate separated. The mixture wasdiluted with methylene chloride (200 mL) and water (200 mL). The layerswere separated, and the organic layer was washed with water (2×50 mL).The organic layer was concentrated to 50 mL, the treated with methanol.aaa15 crystallized as short pale yellow needles (1.19 g, b 1 ^(st)crop). A second crop eventually crystallized from the filtrate (0.66 g).A third crop was obtained by treating the filtrate of the second with afew mLs of water (110 mg).

Example 16

[0129] Synthesis of bbb1

[0130] In an argon filled glove box, aaa15, (98.0 mg, 0.100 mmol),nickel(II)acetonylacetonate (25.7 mg, 0.100 mmol), andtriphenylcarbenium tetrakis(pentafluorophenyl)borate (92.3 mg, 0.100mmol) were weighed to a Schlenk flask. On the Schlenk line, 10 mL drydiethyl ether was added to give a dark red solution. Dry hexane (4 mL)was added and dark crystals separated. The supernatant was removed viafiler paper-tipped cannula. The dark bronze crystals were washed (2×10mL) with a hexane/ether (1/1) mixture, then dried several hours in vacuoto afford 163.3 mg (89%) bbb1.

Example 17

[0131] Synthesis of bbb2

[0132] Ligand aaa9 (1.00 g) was treated with nickel(II)acetonylacetonateand triphenylcarbenium tetrakis(pentafluorophenyl)borate according tothe procedure given in Example 16 to afford 1.71 g (84%) bbb2.

Example 18

[0133] Preparation of a Heterogeneous Catalyst Comprising Ligand a54

[0134] To a vial charged with a54 (23 mg; 44 μmol), Ni(acac)₂ (12.8 mg;49.8 μmol) and Ph₃CB(C₆F₅)₄ (46.2 mg; 50 μmol) was added 0.8 mLdichloromethane. The resulting solution was stirred for a few hours andsubsequently added dropwise to silica (0.5 g; Grace Davison Sylopol2100). Volatiles were then removed under vacuum to give the desiredproduct.

Example 19

[0135] Polymerization of Ethylene Using the Catalyst Prepared in Example18

[0136] A catalyst delivery device was charged with the catalyst preparedin Example 18 (2.5 mg; 0.19 μmol Ni, dispersed in 130 mg Grace DavisonXPO-2402 silica) and fixed to the head of a 1000-mL Parr® reactor. Thedevice was placed under vacuum. The reactor was then charged with NaCl(298 g) that had been dried in vacuum at 130° C. for several hours,closed, evacuated and backfilled with nitrogen five times. The leak rateof the reactor was tested by pressurizing to ca. 200 psi C₂H₄ for 5 min.The reactor was then depressurized, and the salt treated withtrimethylaluminum (10 mL; 2.0 M in hexane) and agitated at 75° C. for 30min. The reactor was subsequently pressurized with ethylene (200 psi)and depressurized to atmospheric pressure three times. The catalyst wasthen introduced in the reactor with appropriate agitation. The reactionwas allowed to proceed for 60 min at 75° C. The reactor was thendepressurized. The polymer was isolated by washing the content of thereactor with hot water. The isolated polymer was further treated with 6M HCl in methanol, rinsed with methanol and dried under vacuum to give5.72 g (1,000,000 TO; 2240 g polymer/g catalyst; GPC: M_(n)=65,400,M_(w)/M_(n)=3.4; ¹H NMR: 10 BP/1000C; T_(m)=122° C.).

Example 20

[0137] Preparation of a Heterogeneous Catalyst Comprising Ligand aa1

[0138] A solution of aa1 (73.6 mg) was dissolved in 0.75 mLdichloromethane and added dropwise to 0.50 g silica (Grace DavisonXPO-2402). The volatiles were removed in vacuo (1.5 h) at roomtemperature. The resulting solid was used as such in subsequentpolymerizations.

Example 21

[0139] Polymerization of Ethylene Using the Catalyst Prepared in Example20

[0140] A catalyst delivery device was charged with the catalyst preparedin Example 20 (3.8 mg; 0.33 μmol Ni) dispersed in 122 mg silica (GraceDavison XPO-2402) and fixed to the head of a 1000-mL Parr® reactor. Thedevice was placed under vacuum. The reactor was then charged with NaCl(315 g) that had been dried in vacuum at 130° C. for several hours,closed, evacuated and backfilled with nitrogen five times. The leak rateof the reactor was tested by pressurizing to ca. 200 psi C₂H₄ for ca. 5min. The reactor was then depressurized, and the salt treated withtrimethylaluminum (10 mL; 2.0 M in hexane) and agitated at 86° C. for 30min. The reactor was subsequently pressurized with ethylene (200 psi)and depressurized to atmospheric pressure three times. The catalyst wasthen introduced in the reactor with appropriate agitation. The reactionwas allowed to proceed for 240 min at 90 C. The reactor was thendepressurized. The polymer was isolated by washing the content of thereactor with hot water. The isolated polymer was further treated with 6M HCl in methanol, rinsed with methanol and dried under vacuum to give8.1 g (850,000 TO; 2100 g polymer/g catalyst; GPC: partially insoluble;¹H NMR: 11.7 BP/1000C; T_(m)=111.2 C).

Example 22

[0141] Polymerization of Ethylene Using the Catalyst Prepared in Example20, with Hydrogen as a Chain-transfer Agent

[0142] A catalyst delivery device was charged with the catalyst preparedin Example 20 (3.8 mg; 0.33 μmol Ni) dispersed in 122 mg silica (GraceDavison XPO-2402) and fixed to the head of a 1000-mL Parr® reactor. Thedevice was placed under vacuum. The reactor was then charged with NaCl(372 g) that had been dried in vacuum at 130° C. for several hours,closed, evacuated and backfilled with nitrogen five times. The salt wasthen treated with trimethylaluminum (10 mL; 2.0 M in hexane) andagitated at 85° C. for 30 min. The reactor was subsequently pressurizedwith ethylene (200 psi) and depressurized to atmospheric pressure threetimes. The catalyst was then introduced in the reactor with appropriateagitation. The reaction was allowed to proceed for 30 min at 85 C. Thereactor was then depressurized and hydrogen (100 mL) was added viasyringe. The reactor was then repressurized with ethylene (200 psi) andthe reaction allowed to proceed for an additional 210 min. The reactorwas depressurized to atmospheric pressure. The polymer was isolated bywashing the content of the reactor with hot water. The resulting polymerwas further treated with 6 M HCl in methanol, rinsed with methanol anddried under vacuum to give 4.41 g (278,000 TO; 686 g polymer/g catalyst;GPC: M_(n)=70,100, M_(w)=589,000. (The chromatogram was bimodal withM_(p)=2,700,000 and 200,000.)

Example 23

[0143] Polymerization of Ethylene Using the Catalyst Prepared in Example20, with Hydrogen as a Chain-transfer Agent

[0144] A catalyst delivery device was charged with the catalyst preparedin Example 20 (14.9 mg; 1.3 μmol Ni) dispersed in 152 mg silica (GraceDavison XPO-2402) and fixed to the head of a 1000-mL Parr® reactor. Thedevice was placed under vacuum. The reactor was then charged with NaCl(363 g) that had been dried in vacuum at 130° C. for several hours,closed, evacuated and backfilled with nitrogen five times. The salt wasthen treated with trimethylaluminum (10 mL; 2.0 M in hexane) andagitated at 85° C. for 30 min. The reactor was subsequently pressurizedwith ethylene (200 psi) and depressurized to atmospheric pressure threetimes. Hydrogen (100 mL) was then syringed in the reactor and thereactor subsequently repressurized to 600 psi ethylene as the catalystwas introduced in the reactor with appropriate agitation. The reactionwas allowed to proceed for 30 min at 89° C. The reactor was thendepressurized to atmospheric pressure. The polymer was isolated bywashing the content of the reactor with hot water. The resulting polymerwas further treated with 6 M HCl in methanol, rinsed with methanol anddried under vacuum to give 26.2 g (1,300,000 TO; 1750 g polymer/gcatalyst; GPC: M_(n)=179,000, M_(w)=717,000).

Example 24

[0145] Preparation of a Tethered Catalyst Derived from Ligand aaa16

[0146] Ph₃CB(C₆F₅)₄ (14.5 mg; 15.7 μmol) was added to a solution ofaaa16 (12.6 mg; 16.0 μmol, prepared by methods similar to thosedescribed above, from the 2,6-diphenyl-4-(4-methoxyphenyl)-aniline, withthe methoxy group being de-O-methylated as the last step) and Ni(acac)₂(4.1 mg; 16 μmol) in acetone to result in a Ni concentration of 9.4μmol/mL. An aliquot (0.75 mL) of the resulting solution was collectedand the volatiles removed in vacuo. The residue was taken up in 1.0 mLdichloromethane, resulting in a Ni concentration of 7.1 μmol/mL. To analiquot of this solution (0.70 mL; 5.0 μmol) was addedtetramethyldisilazane (5.3 μmol) and further diluted withdichloromethane to afford 6.4 μmol/mL. A volume of this solution,equivalent to 1.9 μmol Ni, was diluted with dichloromethane to reach aconcentration of 3.33 μmol/mL. The resulting solution was then addeddropwise to silica (381 mg; Grace Davison XPO-2402). The resulting solidwas stored at room temperature for several hours (ca. 18 h) prior toadding toluene (50 mL). The mixture was stirred for 60 min and thesupernatant removed with a cannula equipped with a filter. The residualsolid was further washed with toluene (2×25 mL) and then dried in vacuoto give an orange solid, used as such in subsequent polymerizationexperiments.

Example 25

[0147] Polymerization of Ethylene Using the Catalyst Prepared in Example24

[0148] A 600-mL Parr® reactor was charged with the catalyst prepared inExample 24. Toluene (150 mL) was added to the reactor beforepressurizing to 200 psi ethylene to saturate the mixture. The reactorwas then depressurized and MMAO type 4 (1.5 mL; 7.14 wt % Al; AkzoNobel) was added. The reactor was repressurized with ethylene (200 psi)and the temperature quickly ramped up to 85° C. The reaction was allowedto proceed under those conditions for 120 min before being quenched byaddition of methanol. The mixture was treated with 6M HCl. The polymerwas collected by filtration and dried in a vacuum oven to give 1.43 g(38 g polyethylene/g catalyst; GPC: M_(n)=1,033,000, M_(w)=2,354,000; ¹HNMR: 12.7 BP/1000 C; T_(m)=114.7° C.).

Example 26

[0149] Ethylene Polymerization with the Nickel Catalyst Derived fromNi(acac)₂, B(C₆F₅)₃, Ph₃C(C₆F₅)₄ and Ligand a52

[0150] A 1 L Parr® autoclave, Model 4520, was dried by heating undervacuum to 180 C at 0.6 torr for 1 h, then cooled and refilled with drynitrogen. The autoclave was charged with dry, deoxygenated hexane (450mL) and 4.0 mL of a 10 wt % solution of MMAO (modified methylalumoxane;23% iso-butylaluminoxane in heptane; 6.42% Al). The reactor was sealedand heated to 80° C. under nitrogen, then sufficient hydrogen was addedto raise the pressure by 15.5 psi, after which sufficient ethylene wasintroduced to raise the total pressure to 300 psig. A sample loopinjector was first purged with 2.0 mL dry, deoxygenated dichloromethane(injected into the reactor), and then used to inject 2.0 mL of a stocksolution (corresponding to 0.60 μmol of pro-catalyst) prepared from17.09 mL of CH₂Cl₂ and 2.91 mL of a stock solution prepared from 42 mgligand a52, 10.1 mg Ni(acac)₂, 20.0 mg B(C₆F₅)₃, 36 mg Ph₃C(C₆F₅)₄ and atotal of 23.964 g CH₂Cl₂ (with the 1^(st) three reagents being combinedin CH₂Cl₂ and then added to a solution of the trityl salt in CH₂Cl₂),followed by 2.0 mL of CH2Cl2, using ethylene gas to force the liquidsinto the autoclave and raise the pressure to ca. 440 psig, after whichtime the reactor was isolated and the pressure was allowed to fall toabout 370 psig. More ethylene was then reintroduced to raise thepressure back to ca. 440 psig, and the cycle was repeated. A secondinjection of 2.0 mL of the same stock solution of pro-catalyst(corresponding to another 0.60 μmol) was made at 17.5 min. The averagepressure was 402 psig, and the average temperature was 80.4° C. After100 min, the reaction was quenched by injection of MeOH, then thereactor was cooled, depressurized and opened. The polyethyleneprecipitate was recovered by filtration and dried in vacuo to obtain50.6 g white polyethylene. A similar experiment without hydrogen,conducted for 80 min, gave 32.92 g polyethylene.

Example 27

[0151] Ethylene Polymerization with bbb1

[0152] A procedure similar to that described in Example 26 was followed,using 450 mL hexane, 4.0 mL MMAO, 14.0 psig hydrogen, sufficientethylene pressure to give 660 psig total pressure, a reactiontemperature of 100° C., a single injection of 0.6 μmol of bbb1 in CH₂Cl₂solution, and a reaction time of 58 min to obtain 27.0 g polyethylene,corresponding to 1.61 (10)⁶ mol C2H4/mol Ni.

Example 28

[0153] Polymerization of Ethylene Using the Catalyst Prepared in Example20, with Hydrogen as a Chain-transfer Agent

[0154] A catalyst delivery device was charged with the catalyst preparedin Example 20 (7.0 mg; 0.61 μmol Ni) dispersed in 160 mg silica (GraceDavison XPO-2402) and fixed to the head of a 1000-mL Parr® reactor. Thedevice was placed under vacuum. The reactor was then charged with NaCl(324 g) that had been dried in vacuum at 130° C. for several hours,closed, evacuated and backfilled with nitrogen five times. The salt wasthen treated with trimethylaluminum (10 mL; 2.0 M in hexane) andagitated at 85° C. for 30 min. The reactor was subsequently pressurizedwith ethylene (200 psi) and depressurized to atmospheric pressure threetimes. Hydrogen (100 mL) was added to the reactor via a syringe. Thecatalyst was then introduced in the reactor with appropriate agitation.The reaction was allowed to proceed for 30 min at 85° C. The reactor wasdepressurized to atmospheric pressure. The polymer was isolated bywashing the content of the reactor with hot water. The resulting polymerwas further treated with 6 M HCl in methanol, rinsed with methanol anddried under vacuum to give 0.67 g (30,000 TO; 73 g polymer/g catalyst;GPC: M_(n)=127,400, M_(w)=463,000; 13.9 BP/1000 C by ¹H NMR).

Example 29

[0155] Polymerization of Ethylene Using the Catalyst Prepared in Example20, with Hydrogen as a Chain-transfer Agent

[0156] A catalyst delivery device was charged with the catalyst preparedin Example 20 (5.5 mg; 0.48 μmol Ni) dispersed in 148 mg silica (GraceDavison XPO-2402) and fixed to the head of a 1000-mL Parr® reactor. Thedevice was placed under vacuum. The reactor was then charged with NaCl(350 g) that had been dried in vacuum at 130° C. for several hours,closed, evacuated and backfilled with nitrogen five times. The salt wasthen treated with trimethylaluminum (10 mL; 2.0 M in hexane) andagitated at 85° C. for 30 min. The reactor was subsequently pressurizedwith ethylene (200 psi) and depressurized to atmospheric pressure threetimes. The catalyst was then introduced in the reactor with appropriateagitation. The reaction was allowed to proceed for 3 min at 85° C. under200 psi ethylene. The reactor was then depressurized and hydrogen (100mL) was syringed in. The reactor was then repressurized with ethylene(200 psi) and the reaction allowed to proceed for a total reaction timeof 120 min. The reactor was depressurized to atmospheric pressure. Thepolymer was isolated by washing the content of the reactor with hotwater. The resulting polymer was further treated with 6 M HCl inmethanol, rinsed with methanol and dried under vacuum to give 2.0 g(140,000 TO; 340 g polymer/g catalyst; GPC: M_(n)=81,600 M_(w)=301,800;12.4 BP/1000 C by ¹H NMR; T_(m) (by DSC)=122.2° C.).

Example 30

[0157] Ethylene Polymerization with the Nickel Catalyst Derived fromNi(acac)₂, B(C₆F₅)₃, Ph₃C(C₆F₅)₄ and Ligand v22

[0158] A 1 L Parr® autoclave, Model 4520, was dried by heating undervacuum to 180° C. at 0.6 torr for 1 h, then cooled and refilled with drynitrogen. The autoclave was charged with dry, deoxygenated hexane (450mL) and 2.0 mL of a 0.25 M solution of triisobutylaluminum in hexanes.The reactor was sealed and heated to 80° C. under nitrogen, thensufficient hydrogen was added to raise the pressure by 8.9 psi, afterwhich sufficient ethylene was introduced to raise the total pressure to250 psig. A sample loop injector was first purged with 2.0 mL dry,deoxygenated dichloromethane (injected into the reactor), and then usedto inject 3×2.0 mL of a stock solution (corresponding to a toal of 3.0μmol of pro-catalyst) prepared from 17.34 mL of CH₂Cl₂ and 2.66 mL of astock solution prepared from 45.3 mg ligand v22, 15.0 mg Ni(acac)₂, 54mg Ph₃C(C₆F₅)₄ and a total of 19.546 g (14.75 mL) CH₂Cl₂, followed by2.0 mL of CH₂Cl₂, using ethylene gas to force the liquids into theautoclave and raise the pressure to ca. 440 psig, after which time thereactor was isolated and the pressure was allowed to fall to about 380psig. More ethylene was then reintroduced to raise the pressure back toca. 440 psig, and the cycle was repeated throughout the experiment togive an average pressure of 404 psig, and an average temperature was80.4° C. After 52 min, the reaction was quenched by injection of MeOH,then the reactor was cooled, depressurized and opened. The polyethylenewas recovered by concentrating the mixture to dryness under vacuum toobtain 13.01 g amorphous polyethylene.

Example 31

[0159] The procedure of Example 30 was followed without change, exceptthe average temperature was 60.1° C., the average pressure was 605 psig,the partial pressure of hydrogen was 4.49 psi, and the total reactiontime was 59.7 min. This afforded 38.6 g amorphous polyethylene,corresponding to 460,000 mol ethylene/mol nickel.

Example 32

[0160] Preparation of a Compound of Formula kk1

[0161] Bis(thioamide) aaa14 is reacted with 1 equivalent ofBu₂Sn(OSO₂CF₃)₂ and 2 equivalents of a non-nucleophilic base, such as2,4,6-tri-tert-butylpyridine to afford a compound of formula kk1, withM¹L_(n)=Bu₂Sn, andAr^(2a)=Ar^(2b)=2,6-di(4-tert-butylphenyl)-4-phenylphenyl.Alternatively, bis(thioamide) aaa14 is reacted with 1 equivalent ofCp₂Zr(NMe₂)₂ to afford a compound of formula kk1, with M¹L_(n)=Cp₂Zr,and Ar^(2a)=Ar^(2b)=2,6-di(4-tert-butylphenyl)-4-phenylphenyl.

Example 33

[0162] Preparation of a Compound of Formula kk2

[0163] 2 equivalents of bis(thioamide) aaa14 are reacted with 1equivalent of SnCl₄ or TiCl₄ and 4 equivalents of a non-nucleophilicbase, such as 2,4,6-tri-tert-butylpyridine to afford a compound offormula kk2, with M¹L_(n)=Sn or Ti, andAr^(2a)=Ar^(2b)=2,6-di(4-tert-butylphenyl)-4-phenylphenyl.Alternatively, 2 equivalents of bis(thioamide) aaa14 are reacted with 1equivalent of Ti(NMe₂)₄ to afford a compound of formula kk2, withM¹L_(n)=Ti, and Ar^(2a)=Ar²=2,6-di(4-tert-butylphenyl)-4-phenylphenyl.

We claim:
 1. A catalyst composition useful for the polymerization ofolefins, which comprises a Group 8-10 metal complex comprising abidentate or variable denticity ligand comprising two nitrogen donoratoms independently substituted by aromatic or heteroaromatic rings,wherein the ortho positions of said rings are substituted by aryl orheteroaryl groups.
 2. A catalyst composition useful for thepolymerization of ethylene, which comprises either (i) a compound offormula ee1, (ii) the reaction product of a metal complex of formula ff1and a second compound Y, or (iii) the reaction product ofNi(1,5-cyclooctadiene)₂, B(C₆F₅)₃, a ligand selected from Set 18, andoptionally an olefin;

wherein: L² is selected from Set 18; T is H, hydrocarbyl, substitutedhydrocarbyl, or other group capable of inserting an olefin; L is anolefin or a neutral donor group capable of being displaced by an olefin;in addition, T and L may be taken together to form a π-allyl or π-benzylgroup; X⁻ is BF₄ ⁻, B(C₆F₅)₄ ⁻, BPh₄ ⁻, or another weakly coordinatinganion; Q and W are each independently fluoro, chloro, bromo or iodo,hydrocarbyl, substituted hydrocarbyl, heteroatom attached hydrocarbyl,heteroatom attached substituted hydrocarbyl, or collectively sulfate, ormay be taken together to form a π-allyl, π-benzyl, or acac group, inwhich case a weakly coordinating counteranion X⁻ is also present; Y iseither (i) a metal hydrocarbyl capable of abstracting acac from ff1 inexchange for alkyl or another group capable of inserting an olefin, (ii)a neutral Lewis acid capable of abstracting Q⁻ or W⁻ from ff1 to form aweakly coordinating anion, a cationic Lewis acid whose counterion is aweakly coordinating anion, or a Bronsted acid whose conjugate base is aweakly coordinating anion, or (iii) a Lewis acid capable of reactingwith a π-allyl or π-benzyl group, or a substituent thereon, in ff1 toinitiate olefin polymerization; R^(3a,b) are each independently H,alkyl, hydrocarbyl, substituted hydrocarbyl, 2,4,6-triphenylphenyl,heteroatom connected hydrocarbyl, heteroatom connected substitutedhydrocarbyl, or fluoroalkyl; and Ar^(1a-d) are each independentlyphenyl, 4-alkylphenyl, 4-tert-butylphenyl, 4-trifluoromethylphenyl,4-hydroxyphenyl, 4-(heteroatom attached hydrocarbyl)-phenyl,4-(heteroatom attached substituted hydrocarbyl)-phenyl, or 1-naphthyl.3. The composition according to claim 2, wherein the metal complex offormula ff1 is selected from Set 19;

wherein: R^(3a,b) are each independently H, methyl, phenyl,4-methoxyphenyl, or 4-tert-butylphenyl; Ar^(1a-d) are each independentlyphenyl, 4-methylphenyl, 4-tert-butylphenyl, 4-trifluoromethylphenyl,1-naphthyl, 2-naphthyl, or 4-phenylphenyl; and X⁻ is BF₄ ⁻, B(C₆F₅)₄ ⁻,BPh₄ ⁻, or another weakly coordinating anion.
 4. The compositionaccording to claim 2, further comprising a solid support.
 5. Thecomposition according to claim 3, wherein Ar^(1a-d) are4-tert-butylphenyl or 1-naphthyl.
 6. A process for the polymerization ofolefins, comprising contacting one or more olefins with the catalystcomposition of claim
 2. 7. The process according to claim 6, wherein thesecond compound Y is trimethylaluminum, and said metal complex iscontacted with the trimethylaluminum in a gas phase olefinpolymerization reactor.
 8. A compound of formula ii1;

wherein: R^(3a,b) are each independently H, methyl, phenyl,4-methoxyphenyl, or 4-tert-butylphenyl; and Ar^(1a-d) are eachindependently phenyl, 4-methylphenyl, 4-tert-butylphenyl,4-trifluoromethylphenyl, 1-naphthyl, 2-naphthyl, or 4-phenylphenyl.
 9. Aprocess for the polymerization of olefins, comprising contacting one ormore olefins with a catalyst composition comprising a Group 8-10transition metal complex which comprises a ligand selected from Set 20;

wherein: R^(2x,y) are each independently H, hydrocarbyl, substitutedhydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connectedsubstituted hydrocarbyl; in addition, R^(2x) and R^(2y) may be linked bya bridging group; R^(3a-f) are each independently H, alkyl, hydrocarbyl,substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatomconnected substituted hydrocarbyl, or fluoroalkyl; and Ar^(1a-d) areeach independently phenyl, 4-alkylphenyl, 4-tert-butylphenyl,4-trifluoromethylphenyl, 4-hydroxyphenyl, 4-(heteroatom attachedhydrocarbyl)-phenyl, 4-(heteroatom attached substitutedhydrocarbyl)-phenyl, 1-naphthyl, 2-naphthyl, 9-anthracenyl, or aryl. 10.A compound selected from Set 21;

wherein: R^(2x,y) are each independently H, hydrocarbyl, substitutedhydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connectedsubstituted hydrocarbyl; in addition, R^(2x) and R^(2y) may be linked bya bridging group; R^(3a-f) are each independently H, alkyl, hydrocarbyl,substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatomconnected substituted hydrocarbyl, or fluoroalkyl; and Ar^(1a-d) areeach independently phenyl, 4-alkylphenyl, 4-tert-butylphenyl,4-trifluoromethylphenyl, 4-hydroxyphenyl, 4-(heteroatom attachedhydrocarbyl)-phenyl, 4-(heteroatom attached substitutedhydrocarbyl)-phenyl, 1-naphthyl, 2-naphthyl, 9-anthracenyl, or aryl. 11.A catalyst composition comprising a Group 8-10 transition metal complexwhich comprises a ligand selected from the formula kk1 or kk2;

wherein: Ar^(2a,b) are each independently aromatic or heteroaromaticgroups wherein the ortho positions are substituted by aryl or heteroarylgroups; M¹ is a metal selected from Groups 3, 4, 5, 6, 13, or 14, or isCu, P or As; and L_(n) are ancillary ligands or groups which satisfy thevalency of M¹, such that M¹ is either a neutral, monoanionic or cationicmetal center, with suitable counterions such that said catalystcomposition has no net charge.
 12. A process for the polymerization ofolefins, comprising contacting one or more olefins with the catalystcomposition of claim 11.